Mixtures of quaternary ammonium dye assistants and dyeing retanned leather therewith



United States Patent "ice 3,273,954 MIXTURES OF QUATERNARY AMMONIUM DYE ASSISTANTS AND DYEING RETANNED LEATH- ER THEREWITH Hubert Wachsmann, Basel-Land, Jakob Bindler, Riehen, and Max Erny, Gelterkinden, Switzerland, assignors to J. R. Geigy A.G., Basel, Switzerland No Drawing. Filed Aug. 26, 1963, Ser. No. 304,662 Claims priority, application Switzerland, Sept. 14, 1962, 10,946/ 62 8 Claims. (Cl. 812) The present invention concerns a process for the dyeing of leather, the dye liquor suitable for the performance of this process as well as, industrial product, the leather dyed by this process.

Leather tanned or re-tanned with vegetable and/or synthetic tanning agents cannot be dyed in sufiicient depth of shade with acid dyestuffs due to its anionic surface charge. To increase the depth of shade of leather dyeings, various cation-active auxiliaries have been tried; however, their use entails a series of drawbacks. Sometimes, these auxiliaries cause precipitations with anionic dyestuffs so that they cannot be used in the dyebath, but only as dyestuif-fixing agents in the after-treatment of dyed leather in a separate bath. To deepen the shade, they can be applied for the same purpose in a prior or intermediate treatment, always requiring a change of bath liquor. As a further drawback, these agents are bound very quickly and predominantly in places on the leather surface where there are greater amounts of tanning agent present so that uneven dyeing results. In addition, cationic recharging of the surface generally leads to disturbances in subsequent anionic fatliquoring.

It has now been found that leather can be dyed in level and deep shades in a single stage process, ie, using only one treatment liquor, which liquor contains both dyestutf and cationic auxiliaries of the particular composition defined below.

The treatment liquor to be used according to the invention must contain at least one anionic dyestufi' and, as shade-deepening agent, a quaternized salt of a condensation product produced from the following components:

(a) an aliphatic monoor polyamine containing one lipop'hilic alkyl or alkenyl radical .per molecule;

(b) ethylene oxide in a molar ratio of at least 10 and preferably not more than 200 per mole of (a); and, optionally (c) styrene oxide and/o1- propylene oxide, in amounts of from 1 to 2 moles per mole of (a).

In addition, the treatment liquor can contain still further auxiliaries used in dyeing or leather treatment.

The components from which the above-mentioned shade-deepening agent according to the invention is obtained, are described more in detail hereinafter.

The aliphatic monoamines and polyamines serving as component (a) in the formation of the said shade'deepening agent must contain one higher alkyl or alkenyl radical preferably with from 10 to 20* carbon atoms, such as the decyl, dodecyl, tetradecyl, hexadecyl, octadecyl or eicosyl or oleyl radical, as lipophilic radical, and from one to six amino nitrogen atoms.

In the polyamine moiety of the shade-deepening agents according to the invention which are derived from polyamines, as component (a), the alkylene chain between two neighboring amino nitrogens is an uninterrupted chain 3,273,954 Patented Sept. 20, 1966 containing from 2 to 3 carbon atoms and is of one of the following configurations:

CH -CH CH CH CH or CH2--CH or it is a chain interrupted by one or two oxygen atoms and has one of the following configurations CH CH -OCH CH or -CH --CH OCH --CH O-CH CH These amines are, therefore, mono-higher alkylor monohigher alkenyl-substituted ammonia, ethylenediamine; propylenediamine, di-ethylenetriamine, triethylenetetramine, diaminodiethyl ether or bis-(aminoethyl)- glycol ether and the like, or mixtures of such amines which are substituted in the aforesaid manner. The proportions of ethylene oxide and, optionally, styrene oxide and/ or propylene oxide as defined are reacted with these amines in a manner as described in French Patent 1,261,- 845 issued April 10, 1961, to l. R. Geigy AG.

The polyglycol ethers obtained are quaternized with the ester of a lower saturated aliphatic alcohol preferably methanol or ethanol or an araliphatic alcohol, particularly benzyl or phenylethyl, lower-alkyl-benzyl, chlorobenzyl or bromobenzyl alcohol with a strong acid, e.g. an ester such as dimethy or diethyl sulfate, ethyl chloride, bromide or iodide or benzyl chloride, p-toluene sulfonic acid methyl or ethyl ester, methane sulfonic acid methyl or ethyl ester, chloroor bromo-acetic acid methyl or ethyl ester, or chloro- 0r bromo-propionic acid methyl or ethyl ester, but preferably with dimethyl sulfate, to form the shade-deepening agent, according to the invention.

Very good shade-deepening and levelling action is obtained by the use of a condensation product of an aliphatic polyamine of the structure defined above containing from 2 to 4 basic nitrogen atoms and an alkyl or alkenyl radical of 10 to 20 carbon atoms, with ethylene oxide in a molar ratio of 10:1 to 200:1 quaternized with a lower alkyl sulfate, tosylate or mesylate.

The polyglycol ether produced from 1 equivalent of octadecyl diethylenetriarnine and 20 equivalents of ethylene oxide and quaternized with dimethyl sulfate has been found to give optimal results.

Examples of other auxiliaries which can be contained in the treatment liquor are analogously quaternized addition products of less than 10 equivalents of ethylene oxide.

According to a further aspect of the invention, still deeper shades on leather are obtained with a dyebath of the type described hereinbefore which contains a shadedeepening mixture consisting of (I) a shade deepening agent of components (a) and (b), and optionally (c), as defined above, and at least one of the following (II) basic fixing agents, used hitherto for after-treatment of dyeings with anionic dyestuffs: on cellulose, namely (1) a quaternary salt of an organic tertiary monoamine having per molecule one amino group and from one to two aliphatic or cycloaliphatic radicals having at least 1-0 and preferably not more than 30 carbon atoms, as the substituent or substituents of the amino nitrogen, the remaining one or two nitrogen bonds being substituted with lower alkyl; such amines being, for instance, N-dodecyl-N,N-dimethylor -dietihyl-amine l-(p-methylphenyl)-l-amino-dodecane quaternized with 'benzylchlorid or with dimethyl sulfate;

(2) condensation products of (a) aliphatic polyamines in particular poly-tertiarypolyamines with from 2 to 5 amino nitrogens and with alkylene chains between neighboring amino nitrogen atoms, which are of one of the configurations and o 11,- H-CH;

especially di-tertiary diamines, e.g. N,N,N',N'-tetramethyl-ethylenediamine with (b) aliphatic dihalides, especially dichlorides, dibromides or di-iodies, the carbon chain of which contains 2 to 6 carbon atoms and is uninterrupted or interrupted by one to two oxygen atoms, in molar ratio of from 2:3 to 3:2, particularly valuable compounds being, for example, the condensation product of 2 moles of N,N,N', N",N"-pentarnethyl-diethylenetriamine and 3 moles of'fl, l3-dichlorodiethyl ether or the condensation product of N,N,N',N'-tetramethyl-ethylenediamine and 1,4-dibromobutane;

(3) peralkylated polyethylene polyamines such as are obtained by polymerisation of ethylene imine, subsequently quaternized With lower alkyl halides, especially chlorides, bromide and iodides, or di(lower alkyl)sulfates.

The production of such quaternized polyethylene polyamines has been described, for instance, in German Patent 960,178, issued March 21, 1957, to Farbenfabriken Bayer AG.

The anionic dyestuffs used in the dyebaths for leather according to the invention are those usual in leather dyeing. They can be of any class of dyestuffs; preferably they are of the easily accessible azo, anthraquinone, phthalocyaninc or nitro class of dyestuffs. Examples of azo dyestuffs are unmetallized or metallized, e.g. copper-, chromiumor cobalt-containing, mono-, disor poly-azo dyestuffs of the benzene-azoor the naphthalene-azo-benzene, -naphthalene, -acenaphthene, -ketomethylene and -heterocyclic, particularly -pyrazol-5-one and -5-aminopyrazole series, examples of anthraquinone dyestuffs are condensation products of 1-amino-2-sulfo-4-bromoanthraquinone or 1,4-dihydroxyanthraquinone with preferably aromatic-amines, in particular with an aniline or phenylene-diamine. These dyestuffs preferably contain acid, water solubilizing groups, especially sulfonic acid groups; in addition they can contain the following substituents: lower alkyl, lower alkoxy, hydroxyl, amino, lower alkanoylamino, lower alkanoyl carbamyl and sulfamyl groups, including N-substituted, preferably monoor dilower alkylor N-phenyl or benzylsubstituted carbamyl or sulfamyl, lower alkoxycarbonyl, phenoxy-sulfonyl, lower alkylphenoxy-sulfonyl, chlorophenoxyor bromophenoxy-sulfonyl, lower alkyl-sulfonyl, phenylsulfonyl, lower alkyl-phenylsulfonyl, chloroor bromo-phenylsulfonyl uitro, cyano, trifiuoromethyl groups, halogens such as fluorine chlorine or bromine, etc.

Apart from the anionic dyestuffs and the shade-deepening agent or shade-deepening mixture, described in the foregoing, the dyebaths according to the invention may also contain further auxiliary agents such as polycondensation products of poly-(halogenoalkyl)-amines and amines, or polycondensation products of w-aminoalkyl halides or w-aminoalkanol sulfates the carbon chain of which can be interrupted by hetero atoms and the amino group of which can be primray, secondary or tertiary, such as quaternized polycondensation products of ,B-aminoethyl halides or of 'y-arninopropyl halides; or quaternary compounds from dimethylamine with epichlorohydrin or with glycerin-1x,oU-dichlorohydrin, or quaternized polycondensation products of carboxylic acid amides or N-monoalkylamides having 4 to 7 carbon atoms and containing, in w-position to the carboxyl group, a halogen atom, in particular quaternized polycondensation products of w-chlorobutyric acid amide or of w-chlorovaleric acid amide with formaldehyde and with compounds containing basic secondary amino groups;

polymeric compounds having the grouping it -N=C I such as are formed, e.g. by treating condensation products of ammonia or of amines or salts thereof and dicyanodiamide with aldehydes, namely formaldehyde, optically in the presence of diand poly-amines.

The leather is treated with the dye liquor to be used according to the invention either in the dye bath at temperatures of 4060 C. for about 45 to preferably not longer than minutes, or by spraying or brushing.

The content in the dye bath of quaternary ammonium compounds as defined under (1) supra, is advantageously up to at least about 0.1 and 3%, and preferably 0.3 to 1.5% by weight, that of any cation-active poly-compounds present such as the basic fixing agents defined under (II) from at least about 0.05 up to not more than 1.5%, and preferably 0.1 to 0.8% calculated on the wet leather which has been pressed out to a water content of about 50%.

By treatment according to the invention, depths of shade on re-tanned leather are obtained which corresponds, without any substantial change in shade, to a dyeing of pure cationic chrome leather. Leather so dyed can be well and cleanly fatliquored subsequently with anionic fats. The water absorption power of the dried leather is only slightly altered so that the adherence of the subsequent coating colour is not made more difiicult.

The following non-limitative examples serve to illustrate the invention further. The temperatures are given therein in degrees Centigrade. Percentages are by weight unless stated otherwise. C.I. means Colour Index, Second Edition, 1956, published by The Society of Dyers & Colourists, Bradford, England, and The American Association of Textile Chemists and Colorists, Lowell, Massachusetts.

Example 1 grams (g.) of re-ta-nned chrome leather (shaved weight) are circulated in a solution of 0.5 g. of the azo dyestufi Acid Black 1 Color Index (C.I.) No. 20,470 and water for 30 minutes at 60 in a small rotating drum. A mixture of 0.4 g. of a condensation product of 1 equivalent octadecyl diethylenetriamine and 20 equivalents of ethylene oxide quaternized with dimethyl sulfate as well as 0.1 g. of polycondensation product of 2 mols of N,N,N,N",N"-pentamethyl diethylenetriamine and 3 mols of ,8,B-dichlorodiethyl ether in 5 ml. of water is added through the hollow shaft and the drum is run for 20 minutes. A further 0.5 g. of the dyestuff mentioned is then added, the drum is again run for 20 minutes, finally 0.3 g. of 85% formic acid in 3 ml. of water are added and the drum is again run for 20 minutes. The leather is then fat-liquored in the usual way in the same bath and finished.

Similarly deep leather dyeings are obtained on replacing the 0.4 g. of condensation product of 1 equivalent octadecyl diethylenetriamine and 20 equivalents of ethylene oxide quaternized with dimethyl sulfate by the same amounts of a condensation product of 1 equivalent oleylamine and 20 equivalents of ethylene oxide, 1 equivalent of styrene oxide and 1 equivalent of propylene oxide quaternized with dimethyl sulfate.

If, in this example, instead of the dyestuff mentioned, a dyestuff mentioned in column 2 of the following Table I is used with otherwise the same procedure, then equally deep leather dyeings are obtained of the shades given in column 3.

TABLE I No. Dyestufi (0.1. name, No. or formula) Shade on leather Aeld Brown 6, 0.1. No. 14625.. Brown. Direct Brown 2, 0.1. N 0. 22311 Do. Acid Orange 24, 0.1. N0. 2017[] Do. Acid Orange 7, 0.1. No. 15510 Orange. Direct Blue 86, 0.1. No. 74180 Titniquoise ue. Direct Orange 17, 0.1. No. 19160.. Orange.

OH SOaH I I=N OH S 0311 -S 03H SOsH E O" 8 Green.

II I O NII-- S -CH:

(I31 i N=O O-N=N- NO:

N Hq-S O 1 I S02NH: O (I) I N N=NO (|)N I CH3 Cl ?OrN(GHa)z (IJHa N=C\ I C-N=N- y 10 Cl-N-C I Orange.

l O V O I i N=NO 1 I CH3 SOr-N(CH3)2 Example 2 condensation product from 2 mols of N,N,N,,N",N"-

Similarly good dyeings are obtained on using 0.4 g. of the polyglycol ether obtained from octadecyltriethylenetetramine and gram-equivalents of ethylene oxide pentarnethyl diethylenetniamine and 3 mols of fifl-dichlorodiethyl ether instead of the, in all, 0.5 g. of the mixture of additives mentioned in Example 1 and on folquaternized with dirnethyl sulfate and 0.1 g. of the polylowing the same procedure.

7 Example 3 Equally advantageous leather dyeings are obtained by using, instead OLf the, in all, 0.5 g. of the mixture of additives mentioned in Example 1, 0.2 g. of the polyglycol ether produced from octadecyl diethylenetriamine and 20 gram-equivalents of ethylene oxide quaternized with diethyl sulfate and 0.1 g. of the polycondensation product of 1,4-dibromobutane and N,N,N.',N-tetramethylenediamine; otherwise following the procedure in Example 1.

Example 4 Also, beautifully rfast dyeings are obtained on replacing the, in all, 0.5 g. of the combination of additives mentioned in Example 1 by 1 g. d the polyglycol ether produced from octadecyl diethylenetriamine and 20 gramequivalents of ethylene oxide quaternized with dimethyl sulfate, and by 0.5 g. of the polyglycol ether obtained by polyaddition of oleylamine with 5 gram-equivalents of ethylene oxide, 1 gram-equivalent of styrene oxide and 1 gram-equivalent of propylene oxide and by otherwise following the same procedure.

Example 5 Beautiful deep leather dyeings are obtained on using the additives mentioned in Example 4 in amounts of 0.5 g. of each instead of 1 g. and 0.5 g. respectively; otherwise the procedure given in Example 1 is followed.

Example 6 Equally beautiful dyeings are obtained by repeating Example 1, but replacing the combination of additives used in Example 1 by 0.4 g. of the polyglycol ether produced from octadecyl propylenediamine or from lauryl diethylenetriamine or from cetyl ethylened-iamine or from stearyl ethylenediamine and 20 gram-equivalents of ethylene oxide quaternized with dimethyl sulfate and by 0.1 g. of l-(p-methylp henyl)-1-aminododecane, quaternized with methyl bromide.

Example 7 The same dyeing effects are also attained by replacing the 0.1 g. of quaternized l-(p-methylphenyl)-l-aminododecane mentioned in Example 6 by the same amounts of N-dodecyl-N,N-dimethylamine quaternized with benzyl chloride or by poly-N-,8 chloroethyl-N,N-diethylamine or by polyethyleneimine quaternized with methyl iodide.

Example 8 100 g. of re-tanned chrome leather (shaved weight) are circulated in a solution of 0.5 g. of Cl. Acid Brown 188 in 500 ml. of water for 30 minutes at 60? in a small rotating drum. 1 g. of the polyglycol ether produced from octadecyl diethylenetriamine and SO gram-equivalents of ethylene oxide quaternized with dimethyl sulfate in 5 ml. of water are added through the hollow shaft of the rotating drum and the drum is run for 20 minutes. Another 0.5 g. of the dyestulf mentioned are then added, the drum is run for another 20 minutes, 0.3 g. of 85% formic acid in 3 ml. of water are finally added and the drum is again rotated for 20 minutes. The leather is then fat-liquored in the usual way in the same bath and finished.

Brown, evenly dyed leather is obtained the depth of shade of which is considerably stronger than an analogous dyeing made without the additive mentioned in the example.

Example 9 By using, instead of the 1 g. of the additive mentioned in Example 8, the same amounts of the analogous polyglycol ethers derived from oleylamine, dodecylamine, hexadecylamine or octadecylarnine and otherwise following the procedure described in Example 8, equally good dyeings are obtained.

We claim:

1. An aqueous dyeing liquor for the dyeing of re-tanned leather in deep color shades, comprising, as essential ingredients (1) an anionic leather dyestuff,

(2) a shade-deepening mixture consisting essentially of (I) the quaternized salt of a condensation product (a) an aliphatic amine containing, per mole cule, from one to six amino nitrogen atoms, one lipophilic N-substituent being a member selected from the group consisting of alkyl with from 10 to 20 carbon atoms and alkenyl with from 10 to 20 carbon atoms, and, between every two adjacent amino nitrogens in amines with more than one nitrogen atom, a linking member selected from the group consisting of CH CH CH -CH CH CH2OH- CH3 -CH -CH OCH CH and CH; -CI-I OCHzCH2OCHzCH2- (b) from 10 IR) 200 moles, per mole of (a),

of ethylene oxide, and (c) from 0 to 2 moles, per mole of (a), of

a member selected from the group consisting of styrene oxide and propylene oxide, quaternized with a member selected from the group consisting of the esters of a strong acid with one of the following: a lower saturated aliphatic alcohol, benzyl alcohol, phenyl-ethyl alcohol, chlorobenzyl alcohol, bromobenzyl alcohol and lower alkyl-benzyl alcohol; and

(a) a quaternary salt of an organic tertiary monoamine having per molecule from 1 to 2 alkyl radicals of at least 10 and not more j than 30 carbon atoms, said alkyl radical being a substituent of the amino nitrogen atom, the remaining nitrogen bonds being substituted with lower alkyl, and (II) a basic fixing agent selected from the group consisting of (b) the condensation product of (a) a polytertiary polyamine with from 2 to 5 amino nitrogen atoms, two to four of which are tertiary nitrogen atoms, and with a linking alkylene chain of 2 to 3 carbon atoms between every two adjacent amino nitrogen atoms, with (5) a straight-chain aliphatic dihalide, the halogen atoms of which are of an atomic number ranging from 17 to 53 and the aliphatic chain of which is of 2 to 6 carbon atoms interrupted by from 0 to 2 oxygen atoms, the molar ratio of (a) to 8) ranging from about 2:3 to 3:2, said quaternizing salt defined under (I) being present in said dyeing liquor in an amount of from about 0.1 to 3% by weight, and said basic fixing agent defined under (II) being present in said dyeing liquor in an amount of from about 005 to not more than 1.5% by weight, calculated on the weight of the Wet leather being dyed which has been pressed out to a water content of about 50% 2. A process for dyeing re-tanned leather in deep color shades, comprising the step of applying to the surface of said leather and aqueous dyeing liquor as defined in claim 1.

3. In a process for dyeing re-tanned leather in deep color shades, the improvement of an aqueous dye liquor (i) introducing into an aqueous dyebath re-tanned leather and a first portion of an anionic leather dyestuff, and dissolving the latter in said dyebath, and maintaining the dyebath at temperature of about 40 to 60 0,

(ii) adding successively to the dyebath, first from about 0.15 to 4.5% by weight calculated on the weight of the leather being dyed, when weighed with a water content of about 50%, of a shade-deepening mixture consisting essentially of (I) the quaternized salt of a condensation product (a) an aliphatic amine containing per molecule from one to six amino nitrogen atoms, one lipophilic N-substituent being a member selected from the group consisting of alkyl with from 10 to 20 carbon atoms and alkenyl with from 10 to 20 carbon atoms, and, between every two adjacent amino nitrogens in amines with more than one nitrogen atom, a linking member selected from the group consisting of (b) from 10 to 200 moles, per mole of (a),

of ethylene oxide, and (c) from O to 2 moles, per mole of (a), of

a member selected from the group consisting of styrene oxide and propylene oxide, quaternized with a member selected from the group consisting of the esters of a strong acid with one of the following: a lower saturated aliphatic alcohol, benzyl alcohol, phenyl-ethyl alcohol, chlorobenzyl alcohol, bromobenzyl alcohol and lower alkyl-benzyl alcohol; and

(II) a basic fixing agent selected from the group consisting of (i) a quaternary salt of an organic tertiary monoamine having per molecule from 1 to 2 alkyl radicals of at least 1 and not more than 30 carbon atoms, said alkyl radical being a substituent of the amino nitrogen atom, the remaining nitrogen bonds being substituted with lower alkyl, and (ii) the condensation product of (a) a polytertiary polyamine with from 2 to 5 amino nitrogen atoms, two to four of which are tertiary nitrogen atoms, and with a linking alkylene chain of 2 to 3 carbon atoms between every two adjacent amino nitrogen atoms, with 8) a straight chain aliphatic dihalide the halogen atoms of which are of an atomic number ranging from 17 to 53 and the aliphatic chain of which is 2 to 6 carbon atoms interrupted by from 0 to 2 oxygen atoms, the molar ratio of (oz) to (/3) ranging from about 2:3 to 3:2, and then a second portion of said anionic leather dyestuff, and maintaining said leather in said dyebath at said temperature range for a total of at least about 45 minutes.

4. A shade-deepening mixture for use in aqueous dyebaths for the dyeing of re-tanned leather with anionic leather dyes, which mixture consists essentially of (I) the quaternized salt of a condensation product of (a) an aliphatic amine containing, per molecule, from one to six amino nitrogen atoms, one lipophilic N-substituent being a member selected from the group consisting of alkyl with from 10 to 20 carbon atoms and alkenyl with from 10 to 20 carbon atoms, and, between every two adjacent amino nitrogens in amines with more than one nitrogen atom, a linking member selected from the group consisting of (b) from 10 to 200 moles, per mole of (a), of

ethylene oxide, and (c) from 0 to 2 moles, per mole of (a), of a member selected from the group consisting of styrene oxide and propylene oxide, quaternized with a member selected from the group consisting of the esters of a strong acid with one of the following: a lower saturated aliphatic alcohol, benzyl alcohol, phenyl-ethyl alcohol, chlorobenzyl alcohol, bromobenzyl alcohol and lower alkyl-benzyl alcohol; and

(II) a basic fixing agent selected from the group consisting of (a) a quaternary salt of an organic tertiary monoamine having per molecule from 1 to 2 alkyl radicals of at least 10 and not more than 30 carbon atoms, said alkyl radical being a substituent of the amino nitrogen atom, the remaining nitrogen bonds being substituted with lower alkyl, and (b) the condensation product of (a) a polytertiary polyamine with from 2 to '5 amino nitrogen atoms, two to four of which are tertiary nitrogen atoms, and with a linking alkylene chain of 2 mo 3 carbon atoms between every two adjacent amino nitrogen atoms, with (,8) a straight-chain aliphatic dihalide, the halogen atoms of which are of an atomic number ranging from 17 to 53 and the aliphatic chain of which is of 2 to 6 carbon atoms interrupted by from (l to 2 oxygen atoms, the molar ratio of (oz) to (,6) ranging from about 2:3 to 3:2, the weight ratio of components (I) and (II) in said mixture ranging from about 1:15 to about 60:1.

5. A shade-deepening mixture as defined in claim 4, wherein the weight ratio of components (I) to (II) in said mixture ranges from about 4:1 to 1:1.

6. A shade-deepening mixture as defined in claim 4, wherein the weight ratio of components (I) to (II) is about 2:1.

7. A shade-deepening mixture for use in aqueous dyebaths for the dyeing of re-tanned leather with anionic leather dyes, which mixture consists essentially of (I) a condensation product of 1 equivalent of octadecyl diethylenetriamine and 20 gram equivalents ethylene oxide, quaternized with dimethyl sulfate, and

(II) a polycondensation product of 2 moles of N,N,N',N",N" pentamethyl diethylene triamine and 3 moles of ,B,,B-dichlorodiethyl ether, in a weight ratio of (I) to (II) equal to about 4:1.

8. A shade-deepening mixture for use in aqueous dyebaths for the dyeing of re-tanned leather with anionic leather dyes, which mixture consists essentially of (I) a condensation product of 1 equivalent of oleylamine with 20 equivalents of ethylene oxide, 1 equivalent of styrene oxide and 1 equivalent. of propylene oxide, quaternized with dimethyl sulfate, and

(II) A polycondensation product of 2 moles of N ,N,N,N",N" pentamethyl diethylene triamine and 3 moles of B,B'-dichlorodiethyl ether, in a Weight ratio of (I) to (II) equal to about 4:1.

(References on following page) References Cited by the Examiner UNITED STATES PATENTS Schoeller 884 Meyer 8--13 X Keller 884 Buehler 843 Casty 854 1 2. FOREIGN PATENTS NORMAN G. TORCHIN, Primary Examiner.

D. LEVY, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3, 273,954 September 20, 1966 Hubert Wachsmann, et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Columns 5 and 6, Table I, insert 7 same Table, formula 8 5 below instead of as in the patent:

Signed and sealed this 24th day of October 1967.

first column, line 7 thereof,

hould appear as shown (SEAL) Attest:

EDWARD J. BRENNER EDWARD M. FLETCHER,JR. Attesting Officer Commissioner of Patents 

1. AN AQUEOUS DYEING LIQUOR FOR THE DYEING OF RE-TANNED LEATHER IN DEEP COLOR SHADES, COMPRISING, AS ESSENTIAL INGREDIENTS (1) AN ANIONIC LEATHER DYSTUFF, (2) A SHADE-DEEPENING MIXTURE CONSISTING ESSENTIALLY OF (I) THE QUANTERNIZED SALT OF A CONDENSATION PRODUCT OF (A) AN ALIPHATIC AMINE CONTAINING, PER MOLECULE, FROM ONE TO SIX AMINO NITROGEN ATOMS, ONE LIPOPHILIC N-SUBSTITUENT BEING A MEMBER SELECTED FROM THE GROUP CONSISTING OF ALKYL WITH FROM 10 TO 20 CARBON ATOMS, ALKENYL WITH FROM 10 TO 20 CARBON ATOMS, AND, BETWEEN EVERY TWO ADJACENT AMINO NITROGENS IN AMINES WITH MORE THAN ONE NITROGEN ATOM, A LINKING MEMBER SELECTED FROM THE GROUP CONSISTING OF 